GB2084982A - Composition and method for inhibiting corrosion - Google Patents

Composition and method for inhibiting corrosion Download PDF

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Publication number
GB2084982A
GB2084982A GB8115671A GB8115671A GB2084982A GB 2084982 A GB2084982 A GB 2084982A GB 8115671 A GB8115671 A GB 8115671A GB 8115671 A GB8115671 A GB 8115671A GB 2084982 A GB2084982 A GB 2084982A
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amine
morpholine
cyclohexylamine
propanol
amino
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GB8115671A
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GB2084982B (en
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Chemed Corp
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Chemed Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/142—Hydroxy amines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Removal Of Specific Substances (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

1 GB 2 084 982 A 1
SPECIFICATION Composition and method for inhibiting corrosion
This invention relates to treating compositions which are useful in inhibiting corrosion in steam condensate systems and other aqueous systems in which the mineral content is relatively low. The purpose of the invention is to provide corrosion protection for metal parts such as steam valves, steam 5 traps, return condensate lines and heat exchangers and, particularly, to prevent pitting and grooving attack of iron based metals and non-ferrous alloys.
More particularly, the present invention is directed to the use of a hydroxylamine compound in combination with one or more volatile, neutralizing amines.
It is well known that steam lines and steam condensate lines are subject to corrosion which is very 10 difficult to control. This corrosion is principally caused by the presence of two impurities in the steam, namely carbon dioxide and oxygen. Carbon dioxide caused the grooving or channeling attack on metal surfaces while pitting attack is typical of oxygen. The carbon dioxide is commonly controlled by the use of neutralizing amines such as cyclohexylamine, morpholine, diethylaminoethanol, dimethylpropanolamine, and 2-amino-1 -methyi-l -propanol. Unlike caustic soda, soda ash and sodium 15. phosphate, these amines are acceptable for steam condensate application because they are sufficiently volatile reaching each area that is reached by steam and carbon dioxide, and they condense and react wherever a condensate forms. The volatility (also known as vapor-liquid distribution ratio) of the amines, however, varies significantly. For example, cyciohexylamine with high distribution ratio (2.6) tends to escape through the vents in the system and is often recommended for low pressure systems, while 20 morpholine with low distribution ratio (0.48) tends to accumulate in the boiler water resulting in substantial loss through the blowdown. Morpholine is often used for high pressure systems.
The primary disadvantage of neutralizing amines is their inability to provide protection against oxygen attack. Many plants do encounter air leakage into the return system and use of the neutralizing amines alone will not completely prevent corrosion under such conditions.
We have found that the combinations of certain hydroxyiamine compounds and one or more neutralizing amines will reduce both the carbon dioxide and oxygen gases that may be present in the steam condensate. Furthermore, the presence of neutralizing amines provides a catalytic effect in the reaction of a hydroxylamine compound and oxygen, making the removal of oxygen fast enough even at relatively)ow temperature for immediate corrosion protection in the steam condensate systems.
Accordingly, the present invention provides a composition which comprises a hydroxylamine compound having the following general formula:
R, R, / N-O-R, wherein IR, R2 and R, are either the same or different and selected from the group consisting of hydrogen, lower alkyl having from say 1 to 8 carbon atoms, and aryl such as phenyl, benzyl and tolyl, or a water 35 soluble salt thereof and a second neutralizing amine, as well as a method of inhibiting corrosion in a steam condensate line which comprises maintaining in solution therein a hydroxylamine compound as defined above and at least one additional neutralizing amine.
Specific examples of hydroxylamine compounds which may usefully be employed include hydroxylamine and oxygen-substituted and nitrogen-substituted derivatives.
The oxygen scavenging activity of N,N-diethylhydroxylamine (DEHA) in combination with neutralizing amines has been compared to the activity of N,N- dimethylhydroxyla mine alone. The effect of neutralizing amines by itself to the dissolved oxygen was also determined.
The tests were performed in the laboratory using a 4.5 liter reaction vessel containing distilled water saturated with dissolved oxygen and 10 ppm CO, A 5 gallon (19 liter) batch of distilled water 45 was saturated with oxygen by bubbling air through a fritted dispersion tube. The carbon dioxide was naturally present in the distilled water.
The 4.5 liter container was filled up with the oxygen-satu rated water containing 10 ppm CO, The water temperature was adjusted at 70 21 F (21 1 'C). The dissolved oxygen was determined by means of a commercially available oxygen meter equipped with a selective membrane electrode. The 50 oxygen meter probe after calibration was inserted into the top of the container. The first test was conducted by injecting 36 ppm N,N-diethylhydroxylarnine. The subsequent decrease in oxygen concentration was measured as a function of time. Similar experiments were performed by using the same amount of DEHA and adding neutralizing amines to pH 8 to 8.5. Other tests with neutralizing amines but without DEHA were conducted to determine the effect of the amines by themselves. The 55 Table illustrates the catalytic activity of the neutralizing amines in promoting the reaction of DEHA and oxygen in a low temperature water containing both dissolved oxygen and carbon dioxide.
2 GB 2 084 982 A 2 TABLE Removal of Oxygen Time minutes Dissolved Oxygen, ppm 02 Ex. 0 15 30 60 90 120 1. N,N-Diethylhydroxyla mine (DEHA) 9.70 8.76 8.08 6.50 5.60 5.40 2. Morpholine (1) 9.43 9.26 8.85 8.70 8.61 8.60 3. Cyclohexylamine (11) 9.50 9.03 8.88 8.76 8.66 8.60 4. Diethylamin oethanol (111) 9.86 9.60 9.57 9.50 9.50 9.50 5. Dimethylpropanolamine (M 9.65 9.04 8.63 8.43 8.39 8.36 6.2-Amino-2-methy]-1-propanol (V) 8.63 8.52 8.45 8.25 8.12 8.12 7. DEHA + 1 8.22 5.54 3.90 1.97 1.23 0.87 8. DEHA + 11 8.60 4.70 2.63 1.05 0.54 0.33 9. DEHA + Ill 9.48 4.53 2.21 0.80 0.42 0.32 10. DEHA + N 8.36 5.30 3.31 1.66 0.92 0.66 11. DEHA + V 8.10 5.45 3.81 2.07 1.36 1.05 12. DEHA + (1 & 11) 9.52 4.70 2.33 0.71 0.31 0.21 13. DEHA + (1, 11, Ill, IV &V) 9.80 3.50 1.40 0.34 0.18 0.13 It is evident from the Table that the combinations of DEHA and one or more neutralizing amines were more effective than the DEHA alone when the water contained both carbon dioxide and oxygen.
As expected, the neutralizing amines alone did not significantly reduce the oxygen content. With the DEHA alone the oxygen was reduced by 44.3% as; compared to 89.4% with a combination of DEHA and 5 morpholine and 98.7% with a combination of DEHA and a mixture of five amines.
In the Table, in Example 12, the weight ratio of 1: 11 was 1:1; and in Example 13, the ratio of 1:11:1II:IV:Vwas MA:0.5:0.5.
DEHA alone is known to be an oxygen scavenger and corrosion inhibitor in boiler systems. We have found, however, that it is relatively slow reacting by itself in condensate lines (see Example 1 in the 10 Table). It is surprising that DEHA can be converted to an effective, fast-acting oxygen scavenger and inhibitor of corrosion due to dissolved oxygen by maintaining an amine in the condensate along with the DEHA.
The following hydroxylamine compounds show similar unexpected oxygen scavenging activities when tested in combination with one or more neutralizing amines.
1 1 3 GB 2 084 982 A 3 Example No.
14. N,N-Dimethylhydroxyla mine 15. N-Butylhydroxylarnine 16. O-Pentylhydroxylamine 17. N,N-Dipropylhydroxylarnine 18. N-Heptyl hydroxyla mine 19. O-Ethyl N,N-dimethylhydroxyla mine 20. N-Benzyihydroxylamine (P-Benzyihydroxylamine) 21. O-Benzyihydroxylamine (a-Benzyihydroxylamine) 22. 0-Methyl N-propylhydroxylarnine 10 23. N-Octyl hydroxyla mine 24. N-Methyl N-propylhydroxylarnine 25. N-Hexylhydroxyla mine At equilibrium operating conditions the level of the hydroxylamine compound e.g DEHA in the condensate is preferably 0.00 1 to 100 ppm (more preferably, about 5 ppm), and the second amine (or 15 amine mix) at 1 to 1,500 ppm (more preferably about 100 ppm).
The components can be added separately or in admixture in a composition as defined above, and can be added to the boiler feed water and/or directly to the condensate lines. When added as a mix, it is preferred that the weight ratio of the hydroxylamine compound:amine is 0.001 to 1A, more preferably about 0.05:1.
One good way to add the composition is first to add the preselected amount of the hydroxylamine compound and after that, add the second amine or amine mix until the pH of the condensate or the like is 8-8.5. This method was used in the runs for the Table.
The amine component is a volatile neutralizing amine. Such amines are well known in the boiler water condensate art. They are conventionally added to react with carbon dioxide dissolved in the 25 condensate. Typical of such amines are morpholine, cyclohexylamine, diethylaminoethanol, di methylpropa nola mine, 2-amino-2-methyi-l -propanol, dimethylpropylamine, benzylamine. Further details are to be found in H. H. Uhfig "Corrosion and Corrosion Control," pp., 252-253, John Wiley & Sons Inc. (1963) Mixtures of amines can be used.

Claims (17)

1. A composition which comprises a hydroxylamine compound having the general formula R1 R2 / N-O-R, where R, R, and R, which are the same or different, represent hydrogen, lower alkyl, aryl or aryl (lower alkyl), or a water-soluble salt thereof, and a second neutralizing amine.
2. A composition according to claim 1 in which the hydroxylamine compound is N,N diethylhydroxylamine.
3. A composition according to claim 1 or 2 in which the weight ratio of hydroxylamine: second amine is 0.001 to 1:1.
4. A composition according to any one of claims 1 to 3, in which the second amine is cyclohexyl a mine, morpholine, diethylaminoethanol, dimethylpropanola mine or 2-amino-2-methyi-2- 40 propanol.
5. A composition according to claim 4 in which the second amine is a mixture of two or more of cyclohexylamine, morpholine, diethylaminoethanol, dimethylpropanolamine or 2-amino-2-methyi-l propanol.
6. A composition according to claim 5 in which the second amine is a mixture of morpholine and 45 cyclohexylamine.
4 GB 2 084 982 A 4
7. A composition according to claim 5 in which the second amine is a mixture of morpholine, cyclohexylamine, diethylaminoethanol, dimethylpropanolamine, and 2-amino-2-methyl- 1 -propanol.
8. A composition according to claim 1 substantially as hereinbefore described.
9. A method of inhibiting corrosion in a steam condensate line which comprises maintaining in solution therein, 0.001 to 100 ppm of a hydroxylamine compound as defined in claim 1 or a watersoluble salt thereof, and 1 to 1,500 ppm of at least one additional neutralizing amine.
10. A method according to claim 9 in which the hydroxylamine compound is N,Ndiethylhydroxylamine.
11. A method according to claim 9 or 10 in which the hydroxylamine is maintained at about 5 ppm and the additional amine at about 100 ppm.
12. A method according to any one of claims 9 to 11 in which the additional amine is cyclohexylamine, morpholine, diethylaminoethanol, dimethylpropanolamine, or 2-amino-2-methyl- 'I propanol.
13. A method according to claim 12 in which the additional amine is a mixture of two or more of cyclohexylamine, morpholine,diethylaminoethanol,dimethylpropanolamine, and 2-amino-2-methyi-l- 15 propanol.
14. A method according to claim 13 in which the additional amine is a mixture of morpholine and cyclohexylamine.
15. A method according to claim 13 in which the additional amine is a mixture of morpholine, cyclohexylamine, diethylaminoethanol, dimethylpropanola mine, and 2-amino- 2-methy]-1 -propanol. 20
16. A method according to any one of claims 9 to 15 in which the hydroxylamine compound is added first and the amine is added to provide a pH from 8 to 8.5
17. A method according to any one of claims 9 to 15 which comprises adding a composition as claimed in any one of claims 1 to 8.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1982. Published by the Patent Office, Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
i f 4
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ES (1) ES505904A0 (en)
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EP0127064A1 (en) * 1983-05-16 1984-12-05 Amchem Products, Inc. Rust prevention in processing cans
FR2560888A1 (en) * 1984-03-06 1985-09-13 Dearborn Chemicals Ltd METHOD AND COMPOSITION FOR INHIBITING CORROSION
EP0297916A1 (en) * 1987-07-01 1989-01-04 W.R. Grace & Co.-Conn. Control of corrosion in aqueous systems
WO2008006855A2 (en) * 2006-07-11 2008-01-17 Taminco Inhibition of corrosion in cooling water system
FR2979915A1 (en) * 2011-09-13 2013-03-15 Ceca Sa CORROSION INHIBITORS OF HYDROCARBON EXTRACTION PORTS TRANSPORT CONDUITS

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US9493715B2 (en) 2012-05-10 2016-11-15 General Electric Company Compounds and methods for inhibiting corrosion in hydrocarbon processing units
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Cited By (9)

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Publication number Priority date Publication date Assignee Title
EP0127064A1 (en) * 1983-05-16 1984-12-05 Amchem Products, Inc. Rust prevention in processing cans
FR2560888A1 (en) * 1984-03-06 1985-09-13 Dearborn Chemicals Ltd METHOD AND COMPOSITION FOR INHIBITING CORROSION
EP0297916A1 (en) * 1987-07-01 1989-01-04 W.R. Grace & Co.-Conn. Control of corrosion in aqueous systems
US4847001A (en) * 1987-07-01 1989-07-11 W. R. Grace & Co.-Conn. Control of corrosion in aqueous systems
WO2008006855A2 (en) * 2006-07-11 2008-01-17 Taminco Inhibition of corrosion in cooling water system
WO2008006855A3 (en) * 2006-07-11 2008-05-29 Taminco Inhibition of corrosion in cooling water system
FR2979915A1 (en) * 2011-09-13 2013-03-15 Ceca Sa CORROSION INHIBITORS OF HYDROCARBON EXTRACTION PORTS TRANSPORT CONDUITS
WO2013038100A1 (en) * 2011-09-13 2013-03-21 Ceca S.A. Inhibitors of top-of-line corrosion of pipelines conveying crudes from extraction of hydrocarbons
US10422043B2 (en) 2011-09-13 2019-09-24 Arkema France Inhibitors of top-of-line corrosion of pipelines conveying crudes from extraction of hydrocarbons

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JPS5942073B2 (en) 1984-10-12
ES8306509A1 (en) 1983-06-01
CA1160035A (en) 1984-01-10
US4350606A (en) 1982-09-21
IT1211085B (en) 1989-09-29
MY8500519A (en) 1985-12-31
IT8123151A0 (en) 1981-07-24
FR2491503B1 (en) 1986-04-18
SE8105747L (en) 1982-04-04
ES505904A0 (en) 1983-06-01
JPS5763364A (en) 1982-04-16
GB2084982B (en) 1983-06-29
DE3136491A1 (en) 1982-06-24
SE449623B (en) 1987-05-11
FR2491503A1 (en) 1982-04-09
DE3136491C2 (en) 1992-01-23

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